The present invention relates to a stain-proofing agent for preventing adherence of stains and a non-aqueous composition for paints containing the stain-proofing agent, and particularly relates to the non-aqueous composition suitable for paints for building materials, civil engineering, heavy duty coating, automobiles, etc.
In recent years, a solvent-soluble fluoroolefincopolymer containing hydroxyl group or carboxyl group has been used as an ultra-high weather resistive coating resin, and the use thereof has been increasing. It is known that copolymers of fluoroolefin with vinyl ether, vinyl ester or the like, which is proposed in, for example, JP-B-60-21686, JP-A-3-121107, JP-A-4-279612 and JP-A-4-28707, are soluble in usual solvent for paints, and in combination use with a curing agent such as isocyanate or melamine, can be baked or cured at normal temperature to form coating films excellent in weather resistance.
However, those coating films have a problem that, when the films are exposed outdoors, staining substances contained in air and in rain water are easily deposited on an adhere easily to a surface of the coating film (problem in stain-proofing property for preventing adherence of stains). In order to improve wipe-off property of carbon stains and marking ink (stain removal property), reaction products of fluoroolefin copolymer and silane compound were investigated in, for example, JP-A-4-173881. Also in U.S. Pat. No. 3,429,845 and JP-A-4-275379, there are proposed compositions of hydroxyl group-containing fluoroolefin copolymers and compounds (hydrolysis product) prepared by adding water and a catalyst (hydrochloric acid, etc.) to a silicate (monomer) or a silicate condensate (oligomer) and then hydrolyzing the mixture in alcohol. However, those compositions cannot offer the effect of improving the above-mentioned stain-proofing property.
Examples of employing a silane compound as a curing moiety as mentioned above are also proposed in JP-B-45-11309, JP-A-5-78612, JP-A-61-258852, JP-A-62-116673, JP-A-64-75575, JP-A-2-232221, JP-A-2-240153, JP-A-4-211482, JP-A-4-65476 and JP-A-4-292677. However, curing is insufficient due to large contents of alcohol and water. On the other hand, since a silicate originally has hydroxyl group or requires high temperature baking, migration of the silicate to the surface of coating film is inhibited. Also there is a problem that since the silane compound has a non-hydrolyzable group, hydrophilic property is insufficient. Due to the mentioned reasons, the stain-proofing property is not improved like the above-mentioned other proposals.
The situation is the same with respect to other paints of acryl, acrylic silicon, inorganic materials or the like, and a coating film having remarkably improved stain-proofing property is scarcely know.
Further, as disclosed in WO94/06870, WO95/02645, JP-A-7-109435, JP-A-7-82520, JP-A-7-136583 and JP-A-7-136584, very recently techniques for improving stain-proofing property by adding an alkyl silicate to paints have come to be known, but the resulting coating films have disadvantages that hydrophilization of the coating film surface (stain-proofing property) cannot be repeatedly obtained, and that appearance and alkali resistance of the coating film are poor.
The present situation is such that though silane compounds are used as a dehydrating agent at the time of polymerizing or dispersing pigments, almost the whole amount of the silane compound reacts with water during the production process and thus, the effect of improving the stain-proofing property of the resulting coating film is scarcely obtained.
An object of the present invention is to provide a non-aqueous composition for paints being capable of forming a coating film which is remarkably excellent in stain-proofing property whereby neither staining substances contained in air nor stains due to rain water adhere to or are deposited on the coating film surface, and to provide a stain-proofing agent for adding to the composition.
The present invention relates to a stain-proofing agent comprising a compound represented by the formula (1): 
wherein n is an integer of 1 to 20, all of R1 are different or at least two of R1 are the same, each is a monovalent organic group having 1 to 1,000 carbon atoms and may contain oxygen atom, nitrogen atom and/or silicon atom, a part or the whole of hydrogen atoms of said organic group may be substituted by fluorine atom or fluorine atom and chlorine atom.
Further the present invention relates to a non-aqueous composition for paints comprising a stain-proofing agent comprising a compound represented by the formula (1): 
wherein n is an integer of 1 to 20, all of R1 are different or at least two of R1 are the same, each is a monovalent organic group having 1 to 1,000 carbon atoms and may contain oxygen atom, nitrogen atom and/or silicon atom, a part or the whole of hydrogen atoms of said organic group may be substituted by fluorine atom or fluorine atom and chlorine atom; a resin; and a curing agent and/or a curing catalyst.
The stain-proofing agent of the present invention is added to paints for preventing staining substances contained in air and stains due to rain water, so-called rain-marking stains, from adhering to a coating film exposed outdoors (for example, coating films on cars, buildings, etc.). In addition thereto, the stain-proofing agent can be used for a resin surface modifier, antistatic agent, water absorption preventing agent or the like.
Though it is not clear why the above mentioned effect can be obtained with the stain-proofing agent, it is presumed that, for example, the stain-proofing agent exists on the surface of a substrate or a product and is hydrolyzed by water in the air, thereby hydrophilizing the surface of the substrate of the substrate or the product. In that state, even if staining substances together with rain water approach the surface, the rain water is attached to the surface more easily than the staining substances and the staining substances are scattered with the rain water, thus causing neither adherence nor deposition of the staining substances on the surface. As the stain-proofing agent has surface-concentrating property, an efficient effect can be expected. It appears that such a function improves the mentioned effect, i.e., the stain-proofing effect, and even if contamination arises, stains are removed easily, i.e., the stain removal effect is improved.
The stain-proofing agent of the present invention may be a compound represented by the formula (1): 
(hereinafter referred to as xe2x80x9ccompound Ixe2x80x9d).
The industrially available compound I is actually a mixture of compounds having a certain range of n, and thus n is represented as an average value.
Also the compound I contains a condensate (oligomer) having a branched structure or cyclic structure in addition to a linear chain structure.
In the formula (1), n is an integer of 1 to 20, preferably 2 to 15, more preferably 4 to 10. When n decreases, a boiling point of the compound is lowered. Therefore, there is a tendency that when the compound is used for preparing a paint and the paint is applied by spray-coating, the compound is easy to vaporize and difficult to remain in a coating film. On the other hand, if n exceeds 20, when the compound is used for paints, there are defects that compatibility with, for example, a resin and curing agent is poor to lower storage stability, that appearance of a coating film is apt to be poor, that viscosity of the paint becomes high, and further that such a compound is difficult to obtain industrially.
It is preferable that the above-mentioned organic group has hydrolyzability and that after the hydrolysis, the organic group preferably has removable properties such as volatility, water solubility and thermal decomposition property.
All of R1 are different or at least two of R1 are the same, each is a monovalent organic group having 1 to 1,000 carbon atoms and may contain oxygen atom, nitrogen atom and/or silicon atom, a part or the whole of hydrogen atoms of said organic group may be substituted by fluorine atom or fluorine atom and chlorine atom.
It is preferable that the number of carbon atoms is from 1 to 100, more preferably from 1 to 16. When the number of carbon atoms decreases, there is a tendency that, for example, when the compound is used for preparing a paint and the paint is stored, storage stability is lowered. When the number of carbon atoms exceeds 1,000, there is a tendency that compatibility with a resin and hydrolyzability are lowered.
Any of the organic groups may be a substituent having a linear chain or a branched chain. When the substituent has fluorine atom, the branched substituent may be preferred from solubility point of view.
The organic group may contain oxygen atom, nitrogen atom and/or silicon atom From the Viewpoint of surface concentrating property, a group containing fluorine atom or a group containing silicon atom which has non-hydrolyzable group is preferred. A trifluoromethyl group-containing group and dimethylsiloxane chain-containing group are further preferred.
A part of hydrogen atoms of the organic group may be substituted by fluorine atom, which leads to a tendency of giving high surface concentrating property.
Also a part of hydrogen atoms of the organic group may be substituted by fluorine atom and chlorine atom, which leads to a tendency of giving high solubility.
As the organic group containing no fluorine atom of R1, preferable is a hydrocarbon group having 1 to 8 carbon atoms, etc. Examples are, for instance, CH3, C2H5, CH3CH2CH2, (CH3)2CH, CH3(CH2)2CH2, CH3CH2CH2CH2CH(C2H5)CH2, a dimethylsiloxane chain-containing group and the like. From the viewpoints of hydrolyzability, removable property, availability and workability, CH3 and C2H5 are preferred and CH3 is further preferred.
The organic group containing fluorine atom of R1 may be a group having the surface concentrating property, and examples are those represented by, for instance, F(CF2)n(CH2)m, (CF3)2CH, H(CF2)n(CH2)m, F(CF2)n(CH2)mCxe2x95x90O, H(CF2)n(CH2)mCxe2x95x90O, (F(CF2)n(CH2)m)2N, ((CF3)2CH)2N, (H(CF2)n(CH2)m)2N, F(CF2)nO(CF(CF3)CF2O)nCF(CF3)Cxe2x95x90O, (F(CF2)n(CH2)m)2Cxe2x95x90N, ((CF3)2CH)2Cxe2x95x90N, (H(CF2)n(CH2)m)2Cxe2x95x90N, F(CF2)n(CH2)mCxe2x95x90ONR3, H(CF2)n(CH2)mCxe2x95x90ONR3, F(CF2)n(CH2)mCxe2x95x90CH2, H(CF2)n(CH2)mCxe2x95x90CH2, F(CF2)n(CH2)mCxe2x95x90CF2 and H(CF2)n(CH2)mCxe2x95x90CF2, wherein m is 0 or an integer of 1 to 6, n is an integer of 1 to 10, R3 represents an alkyl having 1 to 6 carbon atoms, the organic group containing fluorine atom may be a branched chain.
Examples of the fluorine-containing organic groups are, for instance, CF3CH2, CF3CF2CH2, CF3(CF2)2CH2, CF3(CF2)3CH2CH2, (CF3)2CH, CF3(CF2)7CH2CH2, H(CF2)2CH2, H(CF2)3CH2, H(CF2)4CH2, CF3Cxe2x95x90O, CF3CF2Cxe2x95x90O, CF3(CF2)6Cxe2x95x90O, CF3(CF2)7Cxe2x95x90O, and the like. From the viewpoints of surface concentrating property, hydrolyzability and removable property, CF3CH2, CF3CF2CH2, CF3(CF2)2CH2, CF3(CF2)3CH2CH2, CF3Cxe2x95x90O and CF3CF2Cxe2x95x90O are preferred, and CF3CH2 and CF3CF2CH2 are further preferred.
Examples of the compound I are, for instance, 
and the like, wherein m and n are the same as above. From the viewpoints of surface concentrating property, hydrolyzability, removable property and availability, preferable are: 
As a process for synthesizing such a fluorine-containing silicate or its oligomer as the compound I there is disclosed a process in which metallic sodium is used in, for example, U.S. Pat. No. 3,491,134, but there is difficulty in reaction procedures. Also a process disclosed in U.S. Pat. No. 2,777,870 has a problem that it is difficult to obtain starting materials.
In the present invention, there was found a process for synthesizing such a fluorine-containing silicate or its oligomer as the compound I without the problems as mentioned above, and thus the present invention has been completed.
The fluorine-containing silicate can be synthesized by allowing an alkyl silicate such as tetrachlorosilane, tetramethoxysilane or tetraethoxysilane to react with a fluorine-containing organic compound such as a fluorine-containing alcohol, a fluorine-containing carboxylic acid or a metal salt of fluorine-containing carboxylic acid.
The oligomer of the fluorine-containing silicate can be synthesized by allowing a chlorosiloxane compound such as hexachlorodisiloxane, octachlorotrisiloxane or decachlorotetrasiloxane, or an alkoxysiloxane compound such as an oligomer of tetramethoxysilane (for instance, Methyl Silicate 51 available from Colcoat Co., Ltd.) or an oligomer of tetraethoxysilane (for instance, Ethyl Silicate 40 available from Colcoat Co., Ltd.) to react with the above-mentioned fluorine-containing organic compound.
The oligomer of the fluorine-containing silicate can also be synthesized by further condensating, for example, a previously synthesized fluorine-containing silicate (monomer).
As a synthesis of an alkyl silicate containing no fluorine atom, there may be employed, for example, a process disclosed in JP-B-62-918. The process can also be applied to a synthesis of the fluorine-containing silicate.
The synthesis of the fluorine-containing silicate or its oligomer which is used in the present invention is then explained hereinbelow in detail.
As the first synthesis of the fluorine-containing silicate or its oligomer, there is, for example, a process in which a compound represented by the formula (9):
RfOHxe2x80x83xe2x80x83(9) 
wherein Rf is a monovalent organic group having 1 to 1,000 carbon atoms and may contain oxygen atom, nitrogen atom and/or silicon atom, a part or the whole of hydrogen atoms of the organic group is substituted by fluorine atom or fluorine atom and chlorine atom, is allowed to react in the presence or absence of a catalyst, with a compound represented by the formula (10): 
wherein n is an integer of 1 to 20, all of R3 are different or at least two of R3 are the same, each is a monovalent organic group having 1 to 1,000 carbon atoms, to prepare a fluorine-containing silicate or its oligomer represented by the formula (11): 
wherein n, R3 and Rf are the same as above, or represented by the formula (12): 
wherein n and Rf are the same as above.
As the catalyst, it is preferable to use an acid, alkali, organometal compound or metal salt.
In the formula (9), the number of carbon atoms of Rf is preferably from 1 to 100, more preferably from 1 to 16. When the number of carbon atoms decreases, since a difference in boiling point from R3OH which is substituted at the time of synthesis is small, there is a tendency that a substitution ratio is decreased to lower storage stability of the resulting paint. When the number of carbon atoms exceeds 1,000, there is a tendency that solubility of RfOH at the time of synthesis is lowered, and compatibility with a resin and hydrolyzability in the coating film are lowered.
Any of Rf may be a linear or branched substituent. From the viewpoints of solubility at the time of synthesis and solubility at the time of preparing a paint, a branched substituent is preferable.
The Rf may contain oxygen atom, nitrogen atom and/or silicon atom. When Rf contains a silicon atom having non-hydrolyzable group, a dimethylsiloxane chain-containing group is preferred from the viewpoints of easiness of substitution with alcohol and surface concentrating property in application of paints.
When a part of hydrogen atoms of Rf is substituted by fluorine atom, there is a tendency that viscosity of the paint becomes low and that the resulting paint is endowed with high surface concentrating property.
When a part of hydrogen atoms of Rf is substituted by fluorine atom and chlorine atom, there is a tendency that RfOH has a high boiling point and the resulting paint is highly soluble.
The Rf may be a group having the surface concentrating property. Examples are those represented by, for instance, F(CF2)n(CH2)m, (CF3)2CH, H(CF2)n(CH2)m, F(CF2)n(CH2)mCxe2x95x90O, H(CF2)n(CH2)mCxe2x95x90O, (F(CF2)n(CH2)m)2N, ((CF3)2CH)2N, (H(CF2)n(CH2)m)2N, F(CF2)nO(CF(CF3)CF2O)mCF(CF3)Cxe2x95x90O, (F(CF2)n(CH2)m)2Cxe2x95x90N, ((CF3)2CH)2Cxe2x95x90N, (H(CF2)n(CH2)m)2Cxe2x95x90N, F(CF2)n(CH2)mCxe2x95x90ONR3, H(CF2)n(CH2)mCxe2x95x90ONR3, F(CF2)(CH2)mCxe2x95x90CH2, H(CF2)n(CH2)mCxe2x95x90CH2, F(CF2)n(CH2)mCxe2x95x90CF2 and H(CF2)n(CH2)mCxe2x95x90CF2, wherein m is 0 or an integer of 1 to 6, n is an integer of 1 to 10, R3 represents an alkyl having 1 to 6 carbon atoms and may be branched.
Examples of those Rf are, for instance, CF3CH2, CF3CF2CH2, CF3(CF2)2CH2, CF3(CF2)3CH2CH2, (CF3)2CH, CF3(CF2)7CH2CH2, H(CF2)2CH2, H(CF2)3CH2, H(CF2)4CH2, CF3Cxe2x95x90O, CF3CF2Cxe2x95x90O, CF3(CF2)6Cxe2x95x90O, CF3(CF2)7Cxe2x95x90O, and the like. From the viewpoints of availability, handling property, surface concentrating property in the resulting paint, hydrolyzability and removable property, CF3CH2, CF3CF2CH2, CF3(CF2)2CH2, CF3(CF2)3CH2CH2, CF3Cxe2x95x90O and CF3CF2Cxe2x95x90O are preferred, and CH3CH2 and CF3CF2CH2 are further preferred.
In the formula (10), n is an integer of 1 to 10, preferably 2 to 10, further preferably 4 to 6. When n decreases, a boiling point of a starting silane compound becomes low at the time of synthesis and thus the synthesis is difficult. Also since a boiling point of the synthesized compound becomes low, there is a tendency that, for example, when the paint is spray-coated, the compound in the paint is easy to be evaporated and difficult to remain in the coating film. On the other hand, when n exceeds 10, there is a problem with repeatability of a synthesis reaction. Also when preparing a paint, there is a tendency that compatibility with a resin and curing agent is poor to lower storage stability, that appearance of the coating film is apt to be poor, that viscosity becomes high, and further that such a compound is difficult to obtain industrially.
All of R3 are different or at least two of R3 are the same. Each is a monovalent organic group having 1 to 1,000 carbon atoms.
The number of carbon atoms of R3 is preferably from 1 to 100, more preferably from 1 to 16. When the number of carbon atoms decreases, there is a tendency that hydrolytic stability of starting material is poor and storage stability of the resulting paint is lowered. When the number of carbon atoms exceeds 1,000, there is a tendency that solubility of the starting material is lowered and that compatibility with a resin and hydrolyzability in the paint are lowered.
Any of R3 may be a linear or branched substituent. From the viewpoint of solubility at the time of preparing a paint, a branched substituent is preferred.
Examples of R3 are, for instance, CH3, C2H5, CH3CH2CH2, (CH3)2CH, CH3(CH2)2CH2, CH3CH2CH2CH2CH(C2H5)CH2, a dimethylsiloxane chain-containing group and the like. From the viewpoints of easiness of substitution with alcohol, removable property, availability and workability, CH3 and C2H5 are preferred and CH3 is further preferred.
Examples of the compound represented by the formula (10) are, for instance, 
and the like.
From the viewpoints of solubility, removable property and availability, preferable are 
In the first synthesis, a catalyst may not be used. From a point of accelerating the reaction, however, the catalyst such as an acid, alkali, organometal compound or metal salt can be used.
Examples of the catalyst are, for instance, acids or alkalis such as hydrochloric acid, sulfuric acid, acetic acid, para-toluenesulfonic acid, ammonia, trimethylamine, triethylamine, tributylamine, 1,8-diazabicyclo(5.4.0)undecen-7 (DBU), (xe2x88x92)-sparteine, 4-N,N-dimethylaminopyridine, monoethanolamine, triethanolamine, N,N,Nxe2x80x2,Nxe2x80x2-tetramethylethylenediamine, sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, potassium t-butoxide, sodium ethoxide, tetramethylammonium hydroxide, tetramethylammonium hydrogensulfate, tetrabutylammonium hydroxide and tetrabutylammonium hydrogensulfate; organometal compounds or metal salts such as dibutyltindilaurate, dibutyltinacetate, dioctyltinmaleate, tetraisopropyltitanate and tetrabutyltitanate; and the like. From a point that a residual catalyst is easy to be removed from the reaction product, ammonia, trimethylamine and triethylamine are preferred.
An example of the first synthesis process may be carried out in that, first, a 500 ml reaction vessel equipped with a thermometer, reflux pipe and dropping funnel is charged with 0.1 mole of the compound represented by the formula (10).
Then the compound represented by the formula (9) is introduced into the reaction vessel in an amount of 0.01 to 0.4(n+1) mole, preferably 0.1(n+1) to 0.2(n+1) mole. In this case, n is the same as one shown in the formula (10). When the amount of the compound represented by the formula (9) decreases, there is a tendency of a substitution ratio becoming lower. When the amount increases, cost tends to become high.
When a catalyst is used, the catalyst may be added in an amount of 0.01 to 10% by mole, preferably 0.1 to 2% by mole on the basis of silicon atoms in the reaction mixture.
When the amount of the catalyst becomes smaller, there is a tendency of a substitution ratio becoming lower. When the amount becomes larger, there is a tendency that removal of the residual catalyst becomes inconvenient.
Then the inside temperature of the reaction vessel is maintained in the range of 0xc2x0 to 200xc2x0 C., preferably 50xc2x0 to 150xc2x0 C. for 1 to 24 hours, preferably 2 to 10 hours.
When the temperature is lower, there is a tendency of a substitution ratio being lower and when the temperature is higher, there is a tendency that side reaction is easy to occur. When the time is shorter, there is a tendency of a substitution ratio being lower and when the time is longer, there is a tendency that side reaction is easy to occur.
Afterwards, the alcohol and, as the case demands, unreacted starting materials are removed through distillation, then 0.01 to 0.2 mole of a compound represented by the formula (11) or (12) is obtained.
0.05 To 0.2 mole of the compound represented by the formula (11) can be obtained by using 0.2(n+1) to 0.3(n+1) mole of the compound of the formula (9) and 0.5 to 2% by mole of the catalyst under the conditions of a temperature of 50xc2x0 to 150xc2x0 C. and a reaction time of 2 to 6 hours.
0.01 To 0.15 mole of the compound represented by the formula (12) can be obtained by using 0.1(n+1) to 0.2(n+1) mole of the compound of the formula (9) and 0.5 to 2% by mole of the catalyst under the conditions of a temperature of 50xc2x0 to 150xc2x0 C. and a reaction time of 2 to 6 hours.
As the second process for synthesis of the oligomer of the fluorine-containing silicate, there is, for example, a process in which tetrachlorosilane is allowed to react with a compound represented by the formula (9):
RfOHxe2x80x83xe2x80x83(9) 
wherein Rf is a monovalent organic group having 1 to 1,000 carbon atoms and may contain oxygen atom, nitrogen atom and/or silicon atom, a part or the whole of hydrogen atoms of said organic group is substituted by fluorine atom or fluorine atom and chlorine atom, and then the obtained compound represented by (RfO)4Si is subject to condensation in an organic solvent to give an oligomer of a fluorine-containing silicate represented by the formula (12): 
wherein n is an integer of 2 to 20, Rf is the same as above.
It is preferable that the organic solvent is at least one selected from the group consisting of an alcohol solvent, ether solvent, ketone solvent, ester solvent, carboxylic acid solvent and fluorine-containing aromatic solvent.
In the above-mentioned second synthesis process, the number of carbon atoms of Rf in the formula (9) is preferably from 1 to 100, more preferably from 1 to 16. When the number of carbon atoms decreases, there is atendency that hydrolytic stability is decreased to lower storage stability of the resulting paints. When the number of carbon atoms exceeds 1,000, there is a tendency of solubility, compatibility with a resin and hydrolyzability being lowered
Any of Rf may be a linear or branched substituent. From the viewpoints of solubility at the time of synthesis and solubility at the time of preparing a paint, a branched substituent is preferred.
The Rf may contain oxygen atom, nitrogen atom and/or silicon atom. From a point that side reaction is difficult to occur and from the viewpoint of surface concentrating property in application of the paint, a dimethylsiloxane chain-containing group is preferred when a silicon atom having non-hydrolyzable group is contained.
When a part of hydrogen atoms of Rf is substituted by fluorine atom, there is a tendency that viscosity of the paint becomes lower and the paint is endowed with high surface concentrating property.
When a part of hydrogen atoms of Rf is substituted by fluorine atom and chlorine atom, there is a tendency that solubility of starting materials becomes high and the resulting paint is highly soluble.
The Rf may be a group having the surface concentrating property. Examples are those represented by, for instance, F(CF2)n(CH2)m, (CF3)2CH, H(CF2)n(CH2)m, F(CF2)n(CH2)mCxe2x95x90O, H(CF2)n(CH2)mCxe2x95x90O, (F(CF2)n(CH2)m)2N, ((CF3)2CH)2N, (H(CF2)n(CH2)m)2N, F(CF2)nO(CF(CF3)CF2O)mCF(CF3)Cxe2x95x90O, (F(CF2)n(CH2)m)2Cxe2x95x90N, ((CF3)2CH)2Cxe2x95x90N, (H(CF2)n(CH2)m)2Cxe2x95x90N, F(CF2)n(CH2)mCxe2x95x90ONR3, H(CF2)n(CH2)mCxe2x95x90ONR3, F(CF2)n(CH2)mCxe2x95x90CH2, H(CF2)n(CH2)mCxe2x95x90CH2, F(CF2)n(CH2)mCxe2x95x90CF2 and H(CF2)n(CH2)mCxe2x95x90CF2, wherein m is 0 or an integer of 1 to 6, n is an integer of 1 to 10, R3 represents an alkyl having 1 to 6 carbon atoms and may be branched.
Examples of those Rf are, for instance, CF3CH2, CF3CF2CH2, CF3(CF2)2CH2, CF3(CF2)3CH2CH2, (CF3)2CH, CF3(CF2)7CH2CH2, H(CF2)2CH2, H(CF2)3CH2, H(CF2)4CH2, CF3Cxe2x95x90O, CF3CF2Cxe2x95x90O, CF3(CF2)6Cxe2x95x90O, CF3(CF2)7Cxe2x95x90O, and the like. From the viewpoints of availability, surface concentrating property in the resulting paint, hydrolyzability and removable property and from a point that side reaction is difficult to occur, CF3CH2, CF3CF2CH2, CF3(CF2)2CH2, CF3(CF2)3CH2CH2, CF3Cxe2x95x90O and CF3CF2Cxe2x95x90O are preferred, and CH3CH2 and CF3CF2CH2 are further preferred.
In the second synthesis, when the compound represented by the formula (12) is synthesized by subjecting the compound represented by (RfO)4Si to condensation through hydrolysis, since the compound of (RfO)4Si is difficult to be dissolved in water, an organic solvent is added to prevent gelling and to prevent non-uniform reaction.
Examples of the organic solvent are, for instance, alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, t-butanol, octanol, 2,2,2-trifluoroethanol and 2,2,3,3,3-pentafluoropropanol; ether solvents such as tetrahydrofuran, 1,4-dioxane and tetrahydropyran; ketone solvents such as acetone; ester solvents such as 2-methoxyethyl acetate; carboxylic acid solvents such as acetic acid, trifluoroacetic acid and F(CF2)8COOH; fluorine-containing aromatic solvents such as trifluoromethylbenzene and m-bistrifluoromethylbenzene; and the like. From the viewpoint of high solubility, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, tetrahydrofuran, 1,4-dioxane and tetrahydropyran are preferred.
An example of the second synthesis may be carried out in that, first, a 1,000 ml reaction vessel equipped with a thermometer, stirrer, reflux pipe, cooling unit and dropping funnel is charged with 1.0 mole of tetrachlorosilane under nitrogen atmosphere, followed by cooling to not more than 10xc2x0 C.
Then the compound represented by the formula (9) is added dropwise in an amount of 3 to 5 moles, preferably 4 to 4.5 moles through the dropping funnel over 2 to 6 hours. When the amount of the compound of the formula (9) is smaller, there is a tendency that unreacted tetrachlorosilane is easy to remain, and when the amount is larger, cost tends to become higher.
Hydrogen chloride generated by the addition of the compound of the formula (9) is removed from the system through a polyvinyl chloride pipe and then trapped.
The temperature of the reaction mixture rises up to about 10xc2x0 C. to about 15xc2x0 C. Therefore, to complete the reaction, after the above-mentioned addition, the reaction mixture is cooled to about 5xc2x0 C. to about 10xc2x0 C. over 1 to 5 hours and then stirred until the generation of the hydrogen chloride stops.
Then the unreacted compound of the formula (9) is removed through distillation with heating. Through further distillation under reduced pressure, 0.5 to 1.0 mole of the compound represented by (RfO)4Si is obtained.
A 300 ml reaction vessel is charged with 0.15 mole of the obtained compound under nitrogen atmosphere, and a mixed solution comprising 1 to 100 ml, preferably 10 to 80 ml of the above-mentioned organic solvent, 0.01 to 5% by mole of a catalyst on the basis of silicon atom and 0.075 to 0.15 mole of water is added slowly with stirring.
When the amount of the organic solvent is smaller, the reaction tends to be not uniform, and when the amount is larger, reactivity tends to be lower. When the amount of the catalyst is smaller, reactivity tends to be lower, and when the amount is larger, removal of the residual catalyst tends to be difficult. When the amount of water is smaller, the degree of condensation tends to be lower, and when the amount is larger, the degree of condensation tends to be high.
At that time there is a case where white turbidity occurs in the system. Even in such a state, to complete the reaction, the mixture is stirred at 20xc2x0 to 100xc2x0 C. for 1 to 5 hours.
Then the mixture is heated to 50xc2x0 to 150xc2x0 C. to distill off the volatile components to obtain a product comprising 0.015 to 0.15 mole of the compound of the formula (12) as a main component in the reaction vessel.
In the present invention, the inventors found purification method for further increasing a purity of the fluorine-containing silicate or its oligomer obtained by the first synthesis or a purity of the oligomer of the fluorine-containing silicate obtained by the second synthesis, and thus the present invention has been completed.
As the purification method of the fluorine-containing silicate or its oligomer, there is a method wherein, for example, the fluorine-containing silicate or its oligomer is brought into contact with a metal oxide or ion exchange resin to remove impurities from the fluorine-containing silicate or its oligomer.
In order to bring the fluorine-containing silicate or its oligomer into contact with the metal oxide or ion exchange resin, there is a preferred method wherein the silicate or its oligomer is fed through a column filled with the metal oxide or ion exchange resin.
As the purification method, in addition to the method employing the column (column method), there is a preferred method wherein the metal oxide or ion exchange resin is put into the fluorine-containing silicate or its oligomer, stirred and then filtrated (batchwise method).
In the column method and batchwise method, the fluorine-containing silicate or its oligomer may be used as it is by dissolving in an organic solvent such as hexane, xylene, butyl acetate, tetrahydrofuran, diethyl ether, acetone or fluorine-containing alcohol.
The column method and batchwise method are carried out at a temperature of 0xc2x0 to 100xc2x0 C., preferably 20xc2x0 to 30xc2x0 C.
The use of the metal oxide is advantageous from the viewpoint of adsorption of impurities.
The use of the ion exchange resin is advantageous from the viewpoint of recycling capability.
Preferred metal oxide is, for example, a metal oxide having an average particle size of 1 to 10,000 xcexcm, preferably 10 to 5,000 xcexcm and a specific surface area of 0.01 to 100 m2/g, preferably 0.1 to 10 m2/g.
Preferred ion exchange resin is, for example, an ion exchange resin having an average particle size of 1 to 10,000 xcexcm, preferably 10 to 5,000 xcexcm, a specific surface area of 0.01 to 100 m2/g, preferably 0.1 to 10 m2/g and an ion exchange capacity of 0.01 to 1,000 meq/g, preferably 0.1 to 100 meq/g.
Examples of the metal oxide are, for instance, hydrotalcite, magnesia, alumina, silica gel, hydroxyapatite, talc, zeolite, kaolinite, montmorillonite, Molecular Sieve and the like.
Examples of the commercially available metal oxide are, for instance, those available from Kyowa Kagaku Kogyo Kabushiki Kaisha such as Kyowaad 115 (MgO), Kyowaad 200 (Al2O3.XH2O), Kyowaad 300 (2.5MgO.Al2O3.XH2O), Kyowaad 400 (Al2O3.Na2O.XH2O), Kyowaad 500 (Mg6Al2(OH)16CO3.4H2O), Kyowaad 600 (2MgO.6SiO2.XH2O), Kyowaad 700, 715 (Al2O3.9SiO2.XH2O), Kyowaad 815 (Mg(OH)2), Kyowaad 1000 (Mg4.5Al2(OH)13CO3.3.5H2O), Kyowaad 1015 (Mg4.5Al2(OH)13CO3.3.5H2O, Particle size 1.5 mm), Kyowaad 2000 (Mg1xe2x88x92xAlxO1+x/2, x=0.3) and Kyowaad 2015 (Mg1xe2x88x92xAlxO1+x/2, x=0.3, Particle size 1.5 mm) and the like. From the viewpoint of adsorption of impurities, Kyowaad 600 is preferred.
As the ion exchange resin, there are, for example, a cation exchange resin and an anion exchange resin.
Examples of the commercially available ion exchange resin are, for instance, Dowex available from Dow Chemical Co., Ltd., Amberlite available from Rhom and Haas Co., Ltd., Diaion available from Mitsubishi Kagaku Kabushiki Kaisha and the like.
According to the purification method as mentioned above, the fluorine-containing silicate or its oligomer having higher purity can be obtained by removing a trace amount of impurities, for example, the residual catalyst, side reaction product, etc. contained in the fluorine-containing silicate or its oligomer. As a result, storage stability of the silicate or its oligomer, storage stability, pot life, workability and curability of the paints obtained therefrom can be further improved.
When the compound I is used for a paint, resin, film and sheet in the state of being dissolved together with a curing agent in an organic solvent such as xylene and butyl acetate, effects of enhancing stain-proofing property and stain removable property and giving antistatic property and anti-haze property are exhibited.
The non-aqueous composition for paints of the present invention comprises the stain-proofing agent comprising the compound I; resin; curing agent and/or curing catalyst. The coating film obtained from the composition exhibits an effect of giving remarkably excellent stain-proofing property as mentioned above.
Examples of the resin are, for instance, a fluoroolefin copolymer having hydroxyl group and/or carboxyl group, acrylic polyol resin, acrylic silicon resin, fluorine-containing silicone resin, inorganic resin and the like which are solvent-soluble. The fluoroolefin copolymer having hydroxyl group and/or carboxyl group and acrylic polyol resin are preferred from a point that they have been widely used.
In addition to the above resins, there is a fluorine-containing resin (such as a vinylidene fluoride copolymer disclosed in JP-A-4-189879) which is solvent-soluble and has no functional group. The fluorine-containing resin can be blended in the above-mentioned resins having a functional group.
Examples of the fluoroolefin copolymer having hydroxyl group and/or carboxyl group are, for instance, those disclosed in each of JP-B-60-21686, JP-A-3-121107, JP-A-4-279612, JP-A-4-28707 and JP-A-2-232221. A number average molecular weight of the copolymer (measured by GPC) is from 1,000 to 100,000, preferably 1,500 to 30,000. When the molecular weight is less than 1,000, curability and weather resistance tend to be insufficient, and when more than 100,000, there is a tendency that problems arise with respect to workability and coating procedures.
A hydroxyl value of the copolymer is from 0 to 200 (mgKOH/g), preferably 0 to 150 (mgKOH/g). When the hydroxyl value decreases, there is a tendency that curing failure is easy to occur, and when the hydroxyl value exceeds 200 (mgKOH/g), there is a tendency that problem arises with respect to flexibility of a coating film.
An acid value of the copolymer is from 0 to 200 (mgKOH/g), more preferably 0 to 100 (mgKOH/g). When the acid value decreases, there is a tendency that curing failure is easy to occur, and when the acid value exceeds 200 (mgKOH/g), there is a tendency that problem arises with respect to flexibility of a coating film.
As one of the copolymers, there can be used tetrafluoroethylene copolymer from the viewpoints of stain-proofing property, stain removable property and corrosion resistance.
Examples of the copolymer are those commercially available, for instance, Zeffle available from Daikin Industries, Ltd., Lumiflon available from Asahi Glass Kabushiki Kaisha, Cefral Coat available from Central Glass Kabushiki Kaisha, Fluonate available from Dai Nippon Ink Kagaku Kogyo Kabushiki Kaisha, Zaflon available from Toa Gosei Kabushiki Kaisha and the like.
The acrylic polyol resin may be a polymer comprising, for example, the following hydroxyl-containing polymerizable unsaturated monomer (a) and if necessary, other polymerizable unsaturated monomer (b) as monomer components.
As the monomer (a), there can be exemplified a compound represented by the following formulae (2) to (5). 
wherein R4 is hydrogen atom or a hydroxyalkyl group. 
wherein R4 is the same as above. 
wherein Z is hydrogen atom or methyl, m is an integer of 2 to 8, p is an integer of 2 to 18, q is 0 or an integer of 1 to 7. 
wherein Z is the same as above, T1 and T2 are the same or different and each is a divalent hydrocarbon group having 1 to 20 carbon atoms, each of s and v is 0 or an integer of 1 to 10, provided that the sum of s and v is 1 to 10.
The hydroxyalkyl group in the formulae (2) and (3) is one having alkyl moiety of 1 to 6 carbon atoms. Examples are xe2x80x94C2H4OH, xe2x80x94C3H6OH, xe2x80x94C4H8OH and the like.
Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms in the formula (5) are, for instance, 
Examples of the monomer component of the formula (2) are, for instance,
CH2xe2x95x90CHOH, 
CH2xe2x95x90CHO(CH2)4OH 
and the like,
Examples of the monomer component of the formula (3) are, for instance,
CH2xe2x95x90CHCH2OH, 
CH2xe2x95x90CHCH2OCH2CH2OH, 
CH2xe2x95x90CHCH2Oxe2x80x94(CH2CH2O)2xe2x80x94H, 
CH2xe2x95x90CHCH2Oxe2x80x94(CH2CH2O)3xe2x80x94H, 
and the like,
Examples of the monomer component of the formula (4) are, for instance,
CH2xe2x95x90C(CH3)COOC2H4OH, 
CH2xe2x95x90CHCOOC3H6OH, 
and the like,
Examples of the monomer component of the formula (5) are, for instance, 
and the like.
In addition, there can be used an adduct of the hydroxyl-containing unsaturated monomer represented by the formulae (2) to (5) and lactone such as xcex5-caprolactone or xcex3-valerolactone.
Other Polymerizable Unsaturated Monomer (b)
The following (b-1) to (b-9) can be used.
(b-1) Olefin compound: For example, ethylene, propylene, butylene, isoprene, chloroprene and the like.
(b-2) Vinyl ether and allyl ether: For example, linear alkyl vinyl ether such as ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, tert-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, octyl vinyl ether or 4-methyl-1-pentyl vinyl ether; cycloalkyl vinyl ether such as cyclopentyl vinyl ether or cyclohexyl vinyl ether; aryl vinyl ether such as phenyl vinyl ether or o-, m- or p-dimethylphenyl vinyl; arylalkyl vinyl ether such as benzyl vinyl ether or phenethyl vinyl ether; and the like.
(b-3) Vinyl ester and propenyl ester: For example, vinyl ester such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl isocaproate, vinyl pivalate or vinyl caprate; propenyl ester such as isopropenyl acetate or isopropenyl propionate; and the like
(b-4) Acrylate or methacrylate: For example, C1 to 18 alkyl ester of acrylic acid or methacrylic acid such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate or lauryl methacrylate; C2 to 18 alkoxyalkyl ester of acrylic acid or methacrylic acid such as methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate or ethoxybutyl methacrylate; and the like.
(b-5) Aromatic vinyl compound: For example, styrene, xcex1-methylstyrene, vinyltoluene, p-chlorostyrene and the like.
(b-6) Others: Acrylonitrile, methacrylonitrile and the like.
(b-7) Carboxyl-containing monomer: Carboxyl-containing vinyl monomer represented by: 
wherein R5, R6 and R7 are the same or different, and each is hydrogen atom, alkyl, phenyl, carboxyl or ester group, n is 0 or 1, or the formula (7): 
wherein R13 and R14 are the same or different, and each is saturated or unsaturated linear or cyclic alkyl, n is 0 or 1, m is 0 or 1. Examples thereof are, for instance, acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, maleic anhydride, fumaric acid, fumaric acid monoester, vinyl phthalate, vinyl pyromellitate and the like.
(b-8) Epoxy-containing monomer: 
(b-9) Amino-containing monomer: 
The acrylic polyol resin may contain hydroxyl, carboxyl, epoxy or amino.
A hydroxyl value of the acrylic polyol resin is from 0 to 200 (mgKOH/g), preferably 0 to 100 (mgKOH/g). When the hydroxyl value decreases, curing failure tends to occur easily, and when the hydroxyl value exceeds 200 (mgKOH/g), there is a tendency that problem arises withrespect to flexibility of a coating film.
An acid value of the acrylic polyol resin is from 0 to 200 (mgKOH/g), preferably 0 to 100 (mgKOH/g). When the acid value decreases, curing failure tends to occur easily, and when the acid value exceeds 200 (mgKOH/g), there is a tendency that problem arises with respect to flexibility of a coating film.
Commercially available acrylic polyol resin is, for example, Dianal available from Mitsubishi Rayon Kabushiki Kaisha, Acrydic available from Dai Nippon Ink Kagaku Kogyo Kabushiki Kaisha, Hitaloid available from Hitachi Kasei Kogyo Kabushiki Kaisha, Olester available from Mitsui Toatsu Kagaku Kabushiki Kaisha or the like.
The acrylic silicon resin may be one prepared by polymerizing the following acrylic silicon monomer with the compound of the formulae (2) to (5) and/or other polymerizable unsaturated monomer (b).
The acrylic silicon resin is a compound having, in one molecule thereof, at least one silane group and a radical polymerizing unsaturated group. Examples of the radical polymerizing unsaturated group are, for instance: 
and the like,
wherein R8 is hydrogen atom or methyl.
As the silane-containing polymerizable unsaturated monomer having a radical polymerizing unsaturated group of: 
there is, for example, a compound represented by the following formula (8). 
wherein R8 is the same as above, R9 is a hydrocarbon group having 1 to 20 carbon atoms, Y is the same or different and is hydrogen atom, hydroxyl, hydrolyzable group, alkyl having 1 to 8 carbon atoms, aryl or arylalkyl, provided that at least one of Y is hydrogen atom, hydroxyl or hydrolyzable group.
Examples of the compound represented by the formula (8) are, for instance,
xcex3-(meth)acryloxypropyltrimethoxysilane,
xcex3-(meth)acryloxypropyltriethoxysilane,
xcex3-(meth)acryloxypropyltripropoxysilane,
xcex3-(meth)acryloxypropylmethyldimethoxysilane,
xcex3-(meth)acryloxypropylmethyldiethoxysilane,
xcex3-(meth)acryloxypropylmethyldipropoxysilane,
xcex3-(meth)acryloxybutylphenyldimethoxysilane,
xcex3-(meth)acryloxybutylphenyldiethoxysilane,
xcex3-(meth)acryloxybutylphenyldipropoxysilane,
xcex3-(meth)acryloxypropyldimethylmethoxysilane,
xcex3-(meth)acryloxypropyldimethylethoxysilane,
xcex3-(meth) acryloxypropylphenylmethylmethoxysilane,
xcex3-(meth)acryloxypropylphenylmethylethoxysilane,
xcex3-(meth)acryloxypropyltrisilanol,
xcex3-(meth) acryloxypropylmethyldihydroxysilane,
xcex3-(meth)acryloxybutylphenyldihydroxysilane,
xcex3-(meth)acryloxypropyldimethylhydroxysilane,
xcex3-(meth)acryloxypropylphenylmethylhydroxysilane and the like.
The acrylic silicon resin may have a hydrolyzable silyl group, hydroxyl or epoxy.
Commercially available acrylic silicon resin is, for example, Gemlac available from Kaneka Corporation, Kuriyamer available from Sanyo Kasei Kogyo Kabushiki Kaisha or the like.
In the present invention, as the above-mentioned resin, there can be used inorganic materials such as a metal (Si, Ti, Al, etc.) alkoxide containing non-hydrolyzable group, an organopolysiloxane containing non-hydrolyzable group and a metal (Si, Ti, Al, etc.) alkoxide having no fluorine atom.
Commercially available inorganic material is, for example, Ecolton available from Gunze Sangyo Kabushiki Kaisha, Glaska available from Nippon Gosei Rubber Kabushiki Kaisha, Porcelin available from Tohpe Kabushiki Kaisha, Bell Clean and Bell Hard available from Nippon Yushi Kabushiki Kaisha, SH, SR and DC Series available from Toray Dow Corning Silicone Kabushiki Kaisha, KR Series available from Shin-Etsu Kagaku Kogyo Kabushiki Kaisha, Planeact available from Ajinomoto Kabushiki Kaisha, organotitanate available from Nippon Soda Kabushiki Kaisha, aluminium alcolate and aluminium chelate compound available from Kawaken Fine Chemical Kabushiki Kaisha, zirconium alkoxide available from Hokko Kagaku Kabushiki Kaisha, modified silicone oil and MMCA available from Nippon Nuicar Kabushiki Kaisha or the like.
Examples of the fluorine-containing silicone resin are, for instance, those disclosed in JP-A-4-279612 and the like.
As the curing agent, there may be used, for instance, isocyanate compound, blocked isocyanate compound, melamine resin, dibasic acid, silane compound containing non-hydrolyzable group, epoxy resin, acid anhydride or the like. From the viewpoints of weather resistance and acid rain resistance, preferable are isocyanate, blocked isocyanate and epoxy resin.
Examples of the isocyanate compound and blocked isocyanate compound are, for instance, 2,4-tolylene diisocyanate, diphenylmethane-4,4xe2x80x2-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, n-pentane-1,4-diisocyanate, trimers thereof, adducts and biurets thereof, polymers thereof having at least two isocyanate groups, blocked isocyanates and the like. The isocyanate compound and blocked isocyanate compound are not limited to them.
A mixing ratio of the isocyanate to the resin is preferably from 0.5 to 5.0 in NCO/OH (mole ratio), further preferably 0.8 to 1.2. When the isocyanate is of moisture curing type, 1.1 to 1.5 is preferred.
Non-restricted examples of the melamine resin are, for instance, a melamine resin, a methylolated melamine resin obtained by methylolating melamine, an alkyl-etherified melamine resin obtained through etherification of a methylolated melamine by an alcohol such as methanol, ethanol or butanol and the like.
Non-restricted examples of the epoxy compound are, for instance, 
and the like.
Non-restricted examples of the acid anhydride are, for instance, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 1,2-cyclohexyldicarboxylic anhydride, succinic anhydride, maleic anhydride and the like.
Dibasic acids such as fumaric acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and 1,2-cyclohexyldicarboxylic acid are also used as the curing agent.
Examples of the curing catalyst are, for instance, organotin compound, organic acidic phosphate, organotitanate compound, reaction product of acidic phosphate and amine, saturated or unsaturated polycarboxylic acid or its acid anhydride, organic sulfonic acid, amine compound, aluminium chelate compound, titanium chelate compound, zirconium chelate compound and the like.
Examples of the organotin compound are, for instance, dibutyltindilaurate, dibutyltinmaleate, dioctyltinmaleate, dibutyltindiacetate and the like.
Examples of the organic acidic phosphate are, for instance, 
and the like.
Examples of the organotitanate compound are, for instance, titanate such as tetrabutyl titanate, tetraisopropyl titanate or triethanolamine titanate.
Further examples of the amine compound are, for instance, amine compound such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminqpropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl) phenol, morpholine, N-methylmorpholine or 1,8-diazabicyclo(5.4.0)undecen-7 (DBU) and a salt thereof with carboxylic acid; low molecular weight polyamide resin obtained from excess polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound; and the like.
Examples of the chelate compound are, for instance, aluminium tris(acetylacetonate), zirconium tetrakis(acetylacetonate), bis(ethylacetoacetate)titanium diisopropoxide and the like.
The curing catalyst may be used alone or in combination of two or more.
In the present invention, combination of the resin and the curing agent and/or curing catalyst is not particularly limited. Examples of the preferred combination are those mentioned below.
In case of the acrylic polyol resin or the fluoroolefin copolymer having hydroxyl group and/or carboxyl group, when they contain hydroxyl group, the curing agent is the isocyanate compound, blocked isocyanate compound or melamine resin, and when they contain carboxyl group, the curing agent is the melamine resin or epoxy compound. In these systems, the curing catalyst can be used together.
In case of the acrylic silicon resin, fluorine-containing silicone resin or inorganic material, the curing catalyst may be used.
With respect to mixing amount of the resin and the stain-proofing agent having the organic group without fluorine atom, an amount of the stain-proofing agent is from 40 to 80 parts by weight, preferably 50 to 70 parts by weight based on 100 parts by weight of the resin When the amount is less than 40 parts by weight, stain-proofing property tends to be lowered, and when the amount exceeds 80 parts by weight, there is a tendency that appearance of a coating film becomes poor or hardness of the film becomes low and compatibility with the resin is lowered.
With respect to mixing amount of the resin and the stain-proofing agent having the organic group with fluorine atom, an amount of the stain-proofing agent is from 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight based on 100 parts by weight of the resin. When the amount is less than 0.1 part by weight, stain-proofing property tends to be lowered, and when the amount exceeds 50 parts by weight, there is a tendency that appearance of a coating film becomes poor and compatibility with the resin is lowered.
The number of fluorine atoms contained in the group having surface concentrating property is from 1 to 50, and is preferably from 3 to 9 from the viewpoints of hydrolyzability and removable property.
In that case, a content of fluorine atom in the compound I is at least 5%, and is preferably from 15 to 60%, more preferably 25 to 50% from the viewpoints of surface concentrating property and hydrolyzability.
In the present invention, an organic solvent can be mixed to the composition particularly when at least one of the organic groups is the group having surface concentrating property and other organic groups are CH3 and/or C2H5.
Examples of the organic solvent are, for instance, hydrocarbon solvent such as xylene, toluene, Solvesso 100, Solvesso 150 or hexane; ester solvent such as methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, ethylene glycol monobutyl acetate, diethylene glycol monomethyl acetate, diethylene glycol monoethyl acetate, diethylene glycol monobutyl acetate, ethylene glycol acetate or diethylene glycol acetate; ether solvent such as dimethyl ether, diethyl ether, dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether or tetrahydrofuran; ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone or acetone; amide solvent such as N,N-dimethylacetamide, N-methylacetamide, acetamide, N,N-dimethylformamide, N,N-diethylformamide or N-methylformamide; sulfonic acid ester solvent such as dimethylsulfoxide; alcohol solvent such as methanol, ethanol, isopropanol, butanol, ethylene glycol, diethylene glycol, polyethylene glycol (degree of polymerization 3 to 100), polyvinyl alcohol, CF3CH2OH, F(CF2)2CH2OH, (CF3)2CHOH, F(CF2)3CH2OH, F(CF2)4C2H5OH, H(CF2)2CH2OH, H(CF2)3CH2OH or H(CF2)4CH2OH; and the like. From the viewpoints of compatibility, appearance of the coating film and storage stability, preferable are alcohol solvents such as lower alcohol and lower fluorine-containing alcohol.
With respect to mixing amount of the resin and the alcohol solvent, an amount of the alcohol solvent is from 1 to 50 parts by weight based on 100 parts by weight of the resin, preferably from 1 to 25 parts by weight from the viewpoints of curability and appearance of a coating film.
When the curing agent has high reactivity with alcohol like a room temperature curing type isocyanate, the amount of the alcohol solvent is further preferably from 1 to 15 parts by weight, and the preferred alcohol is a secondary or tertiary alcohol.
The non-aqueous composition for paints of the present invention is excellent in solvent solubility, and a formed coating film has high weather resistance and is excellent in stain-proofing property, chemical resistance, optical properties, mechanical properties, adhesion to substrates, resistance to yellowing due to heat, etc. Like usual curing compositions, the non-aqueous composition for paints of the present invention can be applied as paints for indoor use for building materials and interior materials or for outdoor use for building materials, cars, air planes, ships, trains, etc., directly on metals, concrete, plastics or on a primer paint such as wash primer, rust preventive paint, epoxy resin paint, acrylic resin paint and polyester resin paint, and further can be used as a sealing agent and film forming agent.
The above-mentioned composition can be used in various manners, for example, in clear, in solid and in blend with filler.
Various coating methods can be employed, for example, spray coating, brush coating, roller coating, curtain flow and dip coating.
To the non-aqueous composition for paints of the present invention can be added, for example, pigment, pigment dispersing agent, thickener, leveling agent, defoaming agent, auxiliary for film forming, ultraviolet ray absorber, HALS, flatting agent, filler, colloidal silica, fungus preventing agent, silane coupling agent, anti-skinning agent, antioxidant, flame retardant, anti-drip agent, anti-static agent, rust preventing agent and the like.
Examples of the pigment are, for instance, titanium oxide, iron oxide, aluminium metallic pigment, carbon black, sintered pigment, phthalocyanine pigment, organic pigment, extended pigment and the like.
Examples of the titanium oxide are, for instance, Tipaque CR-90, CR-93, CR-95 and CR-97 available from Ishihara Sangyo Kabushiki Kaisha and the like.
Examples of the iron oxide are, for instance, Todacolor 120ED, 140ED, 160ED, KN-R and KN-V available from Toda Kogyo Kabushiki Kaisha, TAROX LL-XLO, HY-100, HY-200, BL-100 and BL-500 available from Titan Kogyo Kabushiki Kaisha and the like.
Examples of the aluminium metallic pigment are, for instance, Alpaste 0100MA, 0700MN 0200M, 0215M, 1950M, 1900M, 1100M, 1109M, 1200M, 8820YF, 7080N, MG600 and 1700N available from Toyo Aluminium, Kabushiki Kaisha and the like.
Examples of the carbon black are, for instance, MA7, MA11, MA100, OIL7B, OIL30B and OIL31B available from Mitsubishi Kagaku Kabushiki Kaisha and the like.
Examples of the sintered pigment are, for instance, Daipyroxide #9510, #9512, #9410 and #9310 available from Dainichi Seika Kabushiki Kaisha and the like.
Examples of the phthalocyanine pigment are, for instance, #5195N and #5370 available from Dainichi Seika Kabushiki Kaisha and the like.
Examples of the extended pigment are, for instance, asbestine, calcium carbonate, precipitated calcium carbonate, clay, kaolin, porcelain clay, aluminium silicate, diatomaceous earth, white carbon, white silica, hydrated fine silica, bentonite, talc, magnesium silicate, magnesium carbonate, baryte powder, barium sulfate, precipitated barium sulfate and the like.
Examples of the pigment dispersing agent are, for instance, those available from BYK Chemie Japan Ltd., such as Anti-Terra-P, Anti-Terra-U, Anti-Terra-203/204, Disperbyk, Disperbyk-101, Disperbyk-110, Disperbykl30, Disperbykl61, Disperbyk-164, Disperbyk-170, Bykumen, BYK-P104/P105, BYK-104S, BYK-240S and Lactimon and the like.
Examples of the leveling agent are, for instance, those available from BYK Chemie Japan Ltd., such as BYK-300, BYK-302, BYK-306, BYK-307, BYK-335, BYK-310, BYK-320, BYK-322, BYK-323, BYK-324, BYK-325, BYK-330, BYK-331, BYK-333, BYK-344, BYK-370, BYK-354, BYK-355 and BYK-358 and the like.
Examples of the thickener are, for instance, Disparlon #6900-20X, #6900-10S, #4200-20 and #4200-10 available from Kusumoto Kasei Kabushiki Kaisha, Bentone SD-1, SD-2, SD-3, #27, #34, #38 and MPA-2000X available from NL Chemicals Kabushiki Kaisha and the like.
Examples of the defoaming agent are, for instance, those available from BYK Chemie Japan Ltd., such as BYK-051, BYK-052, BYK-053, BYK-055, BYK-057, BYK-065, BYK-066, BYK-070, BYK-077, BYK-080, BYK-088, BYK-141 and the like.
Examples of the suitable ultraviolet ray absorber are, for instance, those of benzophenone type and benzotriazole type. Among them, effective benzophenone type absorbers are 2,2xe2x80x2-dihydroxy-4,4xe2x80x2-dimethoxybenzophenone, 2,2xe2x80x2-dihydroxy-4,-methoxybenzophenone and 2,2xe2x80x2,4,4xe2x80x2-tetrahydroxybenzophenone, and effective benzotriazole type absorbers are 2-(2xe2x80x2-hydroxy-5xe2x80x2-methylphenyl)benzotriazole, 2-(2xe2x80x2-hydroxy-5xe2x80x2-METHYLPHENYL)-5,6-dichlorobenzotriazole, 2-(2-hydroxy-5xe2x80x2-tert-butylphenyl)benzotriazole, 2-(2xe2x80x2-hydroxy-3xe2x80x2,5xe2x80x2-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2xe2x80x2-hydroxy-5xe2x80x2-phenylphenyl)-5-chlorobenzotriazole, 2-(2xe2x80x2-hydroxy-3xe2x80x2-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2xe2x80x2-hydroxy-3xe2x80x2,5xe2x80x2-di-tert-butylphenyl)benzotriazole and 2-(2xe2x80x2-hydroxy-5xe2x80x2-tert-octylphenyl)benzotriazole.
Particularly suitable ultraviolet ray absorbers are those represented by the formula (13): 
wherein R10 and R11 are the same or different, and each is hydrogen atom, a lower alkyl group, particularly a branched lower alkyl group or an aryl, particularly phenyl, X is hydrogen atom or a halogen atom, particularly chlorine atom.
Examples of HALS are, for instance, Tinuvin-770, 292, 622123 and 440 available from Ciba Geigy and the like.
Examples of the flatting agent are, for instance, Selidast #3620, #9615A, #9612A, #3715 and #3910, Hoechst Wax PE520 and white carbon which are available from Hoechst Industries Co., Ltd., and the like.
Examples of the silane coupling agent are, for instance, methyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, vinyltrimethoxysilane, 3-(glycidyloxy)propyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylisocyanate, 3-triethdxysilylpropylisocyanate and the like. Preferred silane coupling agents are those having amino group or isocyanate group. Particularly one having the isocyanate group is excellent in recoatability and intercoat adhesion of coating films for repairing. Further more preferable is one having an alkylisocyanate group such as 3-trimethoxysilylpropylisocyanate.
The non-aqueous composition for paints of the present invention can be applied to various substrates. Examples of the substrate are, for instance, those made of metal, cement, plastic, etc.
Examples of the metal substrate are, for instance, iron and chemically treated or plated iron, aluminium and chemically treated aluminium, stainless steel and chemically treated stainless steel and the like.
Examples of the cement substrate are, for instance, cement, lime, gypsum, concrete, cement mortar, asbestos slate, gypsum board and the like.
Examples of the plastic substrate are, for instance, polyvinyl chloride, polyester, polycarbonate, acryl, polyolefin, polystyrene, polyurethane, polyamide, nylon, natural rubber, urethane rubber, ABS resin and the like.
In case of the metal substrate, it is preferable from the viewpoints of corrosion resistance and intercoat adhesion that the non-aqueous composition for paints of the present invention is applied after under coating and intermediate coating as mentioned below.
As the under coat paint, a zinc rich paint is preferred.
Examples of a vehicle for organic zinc rich paint are, for instance, chlorinated rubber, polystyrene resin, silicone resin, combination of epoxy resin-polyamide resin and the like. Examples of a vehicle for inorganic zinc rich paint are, for instance, ethyl silicate, sodium silicate, lithium silicate, potassium silicate, ammonium silicate and the like. The vehicles particularly preferred for the purposes of the present invention are combination of epoxy resin-polyamide resin, ethyl silicate, potassium silicate and lithium silicate.
Examples of other preferred under coat paints and intermediate coat paints are paints obtained by adding a usually employed coloring pigment, extended pigment, antisettling agent, dispersing agent, curing agent, curing accelerator, thinner, solvent, etc. to at least one synthetic resin selected from epoxy resin (including tar- or urethane-modified one), vinyl resin (including tar-modified resin and acrylic resin), chlorinated resin, polyurethane resin and phenol resin, and then kneading.
The above-mentioned epoxy resin is a resin which has two or more epoxy groups in its molecule and is used usually for paints.
As the epoxy resin, there can be cited, for example, bisphenol epoxy resin such as commercially available Epikote 828, 834, 836, 1001, 1004 and DX-255 which are trade names of Shell Kagaku Kabushiki Kaisha, Araldite GY-260 which is trade name of Ciba Geigy, DER 330, 331 and 337 which are trade names of Dow Chemical or Epiclon 800 which is trade name of Dai Nippon Ink Kagaku Kogyo Kabushiki Kaisha; phenol-novolac epoxy resin such as commercially available DEN 431 and 438 which are trade names of Dow Chemical; polyglycol epoxy resin such as commercially available Araldite CT-508 which is trade name of Ciba Geigy or DER-732 and 736 which are trade names of Dow Chemical; ester epoxy resin such as Epiclon 200 and 400 which are trade names of Dai Nippon Ink Kagaku Kogyo Kabushiki Kaisha; and cotton-like aliphatic epoxy resin such as an epoxidated polybutadiene like BF-1000 which is trade name of Nippon Soda Kabushiki Kaisha.
Epoxy compounds easily analogized from the above-mentioned epoxy resin and derivatives of the epoxy resin are also usable similarly and are encompassed within the technical scope of the present invention.
For example, polyol epoxy resin, alicyclic epoxy resin, halogen-containing epoxy resin and the like are encompassed therein.
To the epoxy resin can be mixed bituminous materials such as mineral bitumen, asphaltite, asphaltic pyrobitumen, tar, coal tar, artificial asphalt and pitch.
As the curing agent for the epoxy resin, there can be used those usually used for paints, such as amine adduct and polyamide resin.
As the curing agent, there are cited, for instance, polyamide resins such as commercially available Tohmide Y-25, 245, 2400 and 2500 which are trade names of Fuji Kasei Kogyo Kabushiki Kaisha, Zenamide 2000 and Versamide 115 and 125 which are trade names of Dai-ichi General Kabushiki Kaisha, Sunmide 320, 330 and X2000 which are trade names of Sanwa Kagaku Kabushiki Kaisha, and Epicure 3255 and 4255 which are trade names of Shell Kagaku Kabushiki Kaisha; amine adducts such as Tohmide 238 and Fujicure 202 which are trade names of Fuji Kasei Kogyo Kabushiki Kaisha and Adeca Hardener EH-531 which is trade name of Asahi Denka Kabushiki Kaisha; aliphatic polyamines such as Sunmide T-100, D-100 and P-100 which are trade names of Sanwa Kagaku Kabushiki Kaisha; and heterocyclic diamine derivatives such as Epomate B-002, C-002 and S-005 available from Ajinomoto Kabushiki Kaisha.
An adding amount of the curing agent is about an equivalent to the epoxy resin, namely in the range of about 0.7 to about 1.3 equivalents to 1 equivalent of the epoxy resin.
As the curing agent for the epoxy resin, polyisocyanate can also be used.
Examples of the vinyl resins used in the present invention are, for instance, copolymer comprising one or more of monomers such as vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, styrene, vinyl toluene, vinyl alcohol, acrylic acid, methacrylic acid, maleic anhydride, alkyl acrylate and alkyl methacrylate. Examples thereof are vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, acrylic resin and the like.
A chlorinated rubber resin used in the present invention is chlorinated natural rubber which is a compound containing usually 65 to 68% of chlorine.
The chlorinated rubber can be used in the mixture with rosin, coumarone-indene resin, phenol resin, vinyl chloride resin, petroleum resin, nitrile rubber, chloroprene rubber or alkyd resin.
The chlorinated rubber can also be used in the mixture with plasticizer such as chlorinated paraffin, diphenyl chloride, dioctyl phthalate or tricresyl phosphate.
The polyurethane resin used in the present invention is a composition comprising, as a main component, a compound having two or more active hydrogens in its molecule such as polyester polyol, polyether polyol, polyoxyalkylene glycol or acrylic polyol which is obtained from polybasic acid and polyol, and the above-mentioned curing agent, i.e. polyisocyanate having two or more isocyanate groups in its molecule.
When the substrate is the cement substrate, it is preferable that the non-aqueous composition for paints of the present invention is applied on an under coating and intermediate coating as mentioned below.
As the under coat paint, it is particularly preferable to use multi-layer finish paints such as multi-layer finish paint of non-curable synthetic resin emulsion, multi-layer pattern finish paint of reaction-curable aqueous epoxy resin and multi-layer finish paint of reaction-curable solvent-based epoxy resin. The resin component of the non-curable synthetic resin emulsion includes, for example, acrylic resin, vinyl acetate resin and modified resins thereof. Also the curing system of the reaction-curable aqueous or solvent-based epoxy resin includes, for example, epoxy-polyamine, epoxy-polyamide, epoxy-polyaminepolyamide and the like.
The under coat paint on the cement substrate can be applied by, for example, spray coating method, roller coating method, etc. It appears that a sufficient applying amount is usually from 0.5 to 2.0 kg/m2. In general, drying is carried out usually for 1 to 3 days.
Before applying the under coat paint to the cement substrate, known primer, surface sealer or the like which has been used in general for surface preparation for building can be applied previously. In addition to the above-mentioned under coat paint, the present invention includes direct coating of a sealer of solvent-based epoxy resin or coating of the sealer and then smooth-finishing with isocyanate curing resin paint, etc.
The non-aqueous composition for paints of the present invention can be applied to the under coating film by, for example, roller coating method, brush coating method, spray coating method, etc. An applying amount is from 0.05 to 0.5 kg/m2, preferably from 0.1 to 0.3 kg/m2. A cured coating film can be formed by drying at normal temperature for at least one day.
A repair coating method comprises, for example, applying the non-aqueous composition for paints of the present invention after necessary surface preparation of the existing top coating film on the cement substrate for exterior of buildings.
In the above method, the existing top coating is not particularly limited. The particularly preferred top coating film is one formed by using paints as used for the composition of the present invention, i.e. a non-crosslinkable solvent-based paint such as curable fluorine-containing paint, curable acrylic paint, acrylic silicon paint, carbonyl-hydrazide curable aqueous paint or vinyl acetate-modified acrylic resin paint and a non-crosslinkable aqueous paint such as acrylic resin aqueous paint.
Examples of the carbonyl-hydrazide curable aqueous paint are ones prepared by mixing a water dispersion of a carbonyl-containing copolymer with a hydrazide crosslinking agent and an aqueous polyurethane resin having hydrazine residue (for example, JP-A-4-171683). Between the existing top coating and the cement substrate may have been applied a primer and surfacer or thereon may have been applied multi-layer paints.
The surface preparation to be made, if occasion demands, on the existing top coating can be carried out, for example, by applying a surface treating agent mentioned below. Examples of the preferred surface treating agent are, for instance, a cement type filler or surfacer (for example, cement/synthetic resin emulsion, etc.), reaction-curable resin permeable sealer (for example, epoxy polyamine, epoxy polyamide, etc.), and the like.
The surface preparation can be carried out by applying the surface treating agent by means of, for example, roller, brush, etc. An applying amount of the surface treating agent is, for example, from 0.3 to 2.0 kg/m2 in case of the filler, from 0.1 to 1.0 kg/m2 in case of the surfacer and from 0.01 to 0.5 kg/m2 in case of the permeable sealer.
After the application of the surface treating agent, a polyisocyanate curable solvent-based paint can be further applied by means of, for example, roller coating method, brush coating method or spray coating method. It appears that a sufficient applying amount is from 0.05 to 0.5 kg/m2. The drying of the surface treating agent and polyisocyanate curable solvent-based paint is carried out 1 to 3 times. The application and drying of the non-aqueous composition for paints of the present invention can be carried out in the same manner as mentioned above.
Also in case of the plastic substrate, the non-aqueous composition for paints of the present invention can be applied after the application of the under coating and intermediate coating as used in the metal substrate and cement substrate.
Among the plastic substrates, in case of a plastic film and sheet, there are applying methods, for example, gravure roll coating, doctor blade coating, roll coating, reverse roll coating, air knife coating, etc. In those applying methods, a suitable coating thickness is from 1 to 20 xcexcm, preferably from 5 to 10 xcexcm from the viewpoints of appearance of a coating film and coatability.
Examples of uses of articles coated with the non-aqueous composition for paints of the present invention are, for instance, water-proof sheet for agriculture, water-proof sheet for tunnel, polyvinyl sheet for agriculture, polyvinyl film for agriculture, covering sheet, protection sheet for building, protection sheet for train, mesh sheet, mesh screen, polycarbonate roof, acryl board wall, polycarbonate wall, guardrail, traffic signal, inner wall of tunnel, inner plate for tunnel, road sign, guidance plate, side wall of highway, sound-isolation wall for highway, road light, bridge beam, bridge girder, bridge pier, chimney, wall paper, tatami-mat, floor mat, table cloth, ventilation fan, marking film, geo-membrane, advertisement board, mail box, electric-light pole, tent, car, airplane, ship, train, and the like.
Then the present invention is explained by means of examples and the present invention is not limited to them.